JPS60146874A - Nematodicidal 1-(aryl)thiocarbamoyl-2-(aryl)-3-pyrazolidinones - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to nematicidal compounds for the control of nematodes that adversely affect agricultural crops. More particularly, the present invention relates to novel nematicidal 1-(aryl)thiocarbamoyl-2-(aryl)-3-pyrazolidinones, formulations thereof, and their use for treating nematodes.

The novel compound of the present invention has the following general formula.

where R is hydrogen, alkyl of 1 to 4 carbon atoms, or halogen, R1 and R2 are each hydrogen or alkyl of 1 to 4 carbon atoms, and Ro is hydrogen.

halogen, alkyl of 1 to 4 carbon atoms or 1 carbon atom
~4 alkoxy, and n is 0, 1 or 2.

When n is 2, each R0 group may be the same or different.

The foregoing, the entire specification, and the claims.

The term halogen refers to chlorine, bromine, fluorine, or iodine, preferably chlorine or bromine, and the term lower applied to hydrocarbon groups refers to straight-chain and branched 1-4
means a group having 5 carbon atoms.

The compounds of the invention are best described with reference to formula IA shown below.

JP-A-146874(4) From the above, the compound of the present invention is defined in more detail as a compound of the following formula 1-A.

R is hydrogen, methyl or chloro.

R1 is hydrogen or methyl.

R2 is hydrogen or methyl.

R3 is hydrogen, halogen or methyl.

R4 is hydrogen or halogen.

R5 is hydrogen, halogen or lower alkoxy.

And R6 is hydrogen or halogen.

Of particular interest is the following compound of formula 1-A.

(a) When R" is methyl, R, R2, R' and R"' are each hydrogen, and R5 is hydrogen or bromine, R3 is other than methyl.

(b) When R" is methyl, R, R", R4 and R5 are each hydrogen, and RG is hydrogen or bromine, R3 is other than bromine.

(c) When R'' is methyl and R, R'', R'' and R5 are each hydrogen, R4 and R' cannot both be chlorine.

(-d) When R1 is methyl and R, R2, R' and RG are each hydrogen, R3 and R1' cannot both be chlorine.

This is a compound in the above case.

In the above compound definition, the compound as defined above wherein R, R'' and R2 are each hydrogen, R is methyl or chloro and R1
and R2 are each hydrogen.

A compound in which R1 is methyl and R and R2 are each hydrogen.

Specific examples include compounds in which R2 is methyl and R and R1 are each hydrogen.

The compounds of the present invention may be prepared by the following generally described reactions.

R'' (I) This reaction is suitably carried out in the presence of a base and a solvent. Suitable base/solvent systems include pyridine/toluene and sodium hydride/tetrahydrofuran. Other solvents are known to those skilled in the art. /base systems may also be chosen without departing from the spirit of the invention.

Several methods of making starting material (II) are known in the art. 2-Phenyl-3-pyrazolidinone can be prepared by the method of Earl Eurochenberg Chem, Bar, 26° 2972-2975 (1893). 4-Methyl-2-phenyl-3-pyrazolidinone is described by Kekelmer et al. Chem, Ber, 84.10
(1951) method. 5-Methyl-2-phenyl-3-pyrazolidinone can be obtained from Eruknor etc. Chem,
Ber, 25.759-768 (1892). The remaining 2-(chloro- or methyl-substituted phenyl)-3-pyrazolidinone was prepared by Hideran et al. J, Pra
kt, Chem, 313.1173 (1973
) can be constructed by appropriate modification of the method. The above literature references are hereby incorporated by reference.

The following examples illustrate the preparation of the above compounds.

Example 1 Synthesis of l-(4-chlorophenyl)thiocarbamoyl-2-phenyl-3-pyrazolidinone (compound 1) 15m
2.11 g (0,013 mol) of 2-phenyl-3-pyrazolidinone in toluene of Q, 2.21 g (
A mixture of 0.013 mol) of 4-chlorophenylisothiocyanate and 0.5 mQ of pyridine is heated at reflux for 9 hours. The reaction mixture is cooled to room temperature to form a crystalline precipitate. The crystal precipitate was collected by filtration and 3.92 g 1-(4-chlorophenylthiocarbamoyl)-2-phenyl-3-
Produces virazolidinone. Melting point 136-139°C.

Calculated value of CI6 H14CIN 30S C'57.92 H4,25N 12.66S
9.66 Ct 10.69 Actual value C58,01!14.22 N 12.79S
9.76 C110,76 Compound numbers 18-27 characterized in Table 1 are Example 1
It is synthesized by the following method.

Example 2 l-(4-chlorophenyl)thiocarbamoyl-2-(
4-chlorophenyl)-3-pyrazolidinone (compound 1
4) of 1.6 g (0,008 mol) of 2-(4-
A solution of chlorophenyl)-3-pyrazolidinone in 8 mQ dry tetrahydrofuran at room temperature (0.4 g
,009 mol) of sodium hydride (55% suspension in oil, oil removed by washing with hexane) in a stirred mixture. After complete addition, the reaction mixture was heated at 50° C. until gas evolution ceased. It was then cooled to room temperature. 1.4 g (0,008 mol) of 4 in 8 mQ of tetrahydrofuran
- A solution of chlorophenylisothiocyanate is added to the reaction mixture and the resulting mixture is mixed for 14 hours at room temperature.

Saturated ammonium chloride aqueous solution was added into the reaction mixture, and the whole was extracted with ethyl acetate. The organic extract was washed with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate,
Filtered. The solvent was removed under reduced pressure to leave a solid residue. The solid was purified by recrystallization with ethanol to obtain 1.4 g of 1-(4-
Chlorophenyl)thiocarbamoyl-2-(4-chlorophenyl)-3-pyrazolidinone was obtained. Melting point 121~
124℃.

Analysis Calculated value of C,611,4N30SC12 C52
, 47I+ 3.58 No, 47S 8.75 C
119,36 Actual value C52,1983,49N 11.47S 8
．． 62 C119,25 Compounds 2 to 17 whose properties are shown in Table 1 were prepared by the method of Example 2.

The starting material 2-(4-chlorophenyl)-3-pyrazolidinone in Examples 1 and 2 can be prepared as shown in the following examples.

Example 3 Synthesis of 2-(4-chlorophenyl)-3-pyrazolidinone 8.9 g (0.05 mmol) of sodium bicarbonate was added to a stirred solution of 4.2 g (0.05 mmol) of sodium bicarbonate in 25 mQ of water. (4-chlorophenyl)hydrazine hydrochloride was added dropwise. The mixture was stirred until gas evolution ceased after complete addition. To this mixture was added s, s g (o, 1 mol) of acrylonitrile, and the total Heated at ℃ for 4.5 hours.

The mixture was cooled and added to a solution of 9.8 g concentrated sulfuric acid in 29 mQ water at room temperature. The resulting mixture was heated at 40° C. for 1 hour and then at reflux for 2.5 hours. The mixture was cooled and added to a solution of 7.8 g of sodium hydroxide in 11 mA water cooled in a water bath and stirred for 1 hour after complete addition. A precipitate formed and was collected by filtration. Wash the filter cake with water and dry under reduced pressure.

Purified by recrystallization with ethanol to obtain 2.78 g of 2-(4
-chlorophenyl)-3-pyrazolidinone was produced.

Melting point: 120-122°C.

Analysis Calculated value of C9H9N20C1 C54,97H4,61N 14.25C11
B, G3 Actual value C54,65H/1.63N]/1.08
C117,93 Recognizing that like many pesticides, the nematicides of the present invention are generally not applied at full strength, and that the formulation of the poison and the method of application will affect the activity of the substance.

Agronomically acceptable carriers commonly used to facilitate the dispersion of the active ingredient are incorporated into the formulation, along with various additives and optionally other active ingredients. The compounds of the invention can be applied, for example, as powders or liquids.

The choice of application method will vary depending on the nematode species and environmental factors at the particular infestation site. Therefore.

Compounds include granules, powders (dust), hydrated powders (hydrating agents),
It can be formulated as an emulsifiable concentrate, solution-2-dispersion, controlled release composition, etc.

Typical formulations will vary widely in concentration of active ingredient depending on the particular reagents used, the excipients and carriers used, other active ingredients and the desired method of application. With these factors in mind, the active ingredients of a typical formulation are suitably present in a concentration of, for example, from about 0.5% to about 99.5% by weight of the formulation. Substantially inert ingredients such as auxiliaries, diluents, and carriers constitute from about 99.5% to about 0.5% by weight of the formulation. If used in a formulation, surfactants can be present in varying concentrations, with 1 to 30% by weight being suitable. Provided below is a general description of exemplary formulations that can be used in the nematicide dispersions of the present invention.

Dusts include the active ingredient and a finely divided solid carrier and/or diluent9, such as talc, neutral viscosity, kieselguhr, pyrophyllite, chalk, diatomaceous earth.

Calcium phosphate, calcium carbonate and magnesium carbonate,
It is a mixture of sulfur dilime, small grain powder and other organic and inorganic solid carriers. These finely ground formulations generally have an average particle size of less than about 50 microns (325 mesh US standard sieve system). In many cases.

The active ingredient is present in the powder formulation at 1-15% and sometimes 1-15%.
Present at a concentration of about 30%, the remainder of the composition is typically one or more agriculturally acceptable inert materials, such as auxiliaries, carriers, or diluents.

Irrigation powders (wettable powders) are also useful formulations for these nematicides and are in the form of finely divided granules that are easily dispersed in water or other liquid vehicles. The hydrated powder is ultimately applied to plants as a dry dust or a dispersion in water or other liquid.

Typical carriers for water application powders include Fuller's earth, kaolin clay, and silica.

and other highly absorbent or adsorbent inorganic diluents.

The concentration of active ingredient in the water conservancy powder depends on the physical properties of the active ingredient and the adsorption properties of the carrier. Liquids and low-melting solids (melting point <100°C) have concentrations ranging from 5 to 50% by weight, usually 1
Suitably it is formulated in a concentration range of 0-30%, with high melting point solids (melting point >100°C) being formulated in a range of 5-95% by weight, usually 50-85%. Agriculturally acceptable carriers or diluents often contain small amounts of surfactants to facilitate wetting and dispersion and suspension, which make up the remainder of the formulation.

Microcapsules or other controlled release formulations can be used in the nematicide of the present invention for the control of nematodes.

Emulsifiable concentrates (ECs) are generally homogeneous liquid compositions containing an active ingredient dissolved in a liquid carrier. A commonly used liquid carrier is xylene.

Includes heavy aromatic naphtha, isophorone, and other non-volatile or slightly volatile organic solvents.

For nematicide applications, these concentrates are dispersed in water or other liquid excipients to form emulsions.

Usually applied as a spray to the area to be treated.

The concentration of essential active ingredients in the EC varies depending on the method by which the composition is applied, but generally ranges from 0.5 to 95% of the active ingredient, often 10 to 80%, but the remaining 99.5%.
~5% is surfactant and liquid carrier.

Flowables are similar to EC, only the active ingredient is suspended in a liquid carrier, typically water. Flowable agents, like EC, contain small amounts of surfactants.

The active ingredient may range from 0.5% to 95% by weight of the composition, but often from 10% to 50%. For application, flowable agents can be diluted in water or other liquid vehicles and are usually applied as a spray to the area to be treated.

Typical hydrated 9 dispersions used in nematicidal formulations.

Or emulsifiers include alkyl and alkylaryl sulfonates and sulfates and their sodium salts, alkylaryl polyether alcohols, sulfated higher alcohols, polyethylene oxide, sulfonated animal and vegetable oils, sulfonated petroleum, fatty acid esters of polyhydric alcohols,
and ethylene oxide addition products of such esters, and addition products of long chain mercaptans and ethylene oxide. Many other types of useful surfactants are commercially available. When used, surfactants usually constitute 1 to 15% by weight of the nematicidal composition.

Other useful formulations include simple solutions of the active ingredient in relatively non-volatile solvents such as corn oil, kerosene, propylene glycol or other organic solvents. This type of formulation is particularly useful for very low volume applications.

Nematicide concentrations at working dilutions usually range from about 2 to about 0.1%. Many spray, dusting, and controlled release composition variations can be used in the art, substituting or adding the compounds of the invention in compositions known or obvious in the art.

Nematicidal compositions are formulated and applied with other active ingredients, including other nematicides, insecticides, acaricides, fungicides, plant conditioners, herbicides, and fertilizers.

Nematicidally effective amounts must be applied in applying the above chemicals. Application rate is compound selection.

Although varying widely depending on the formulation and mode of application, the plant species being protected, and the planting density, suitable application rates are from 0.5 to 25 kg per heftare, preferably from 1 to about 20 kg per heftare. within the range of

Trees and vines, e.g. at least 5 per hectare
kg per hectare, whereas annuals such as corn require considerably lower application rates, e.g.
kg.

The compounds of the invention are normally applied by placing the formulation into the soil or infested area where the agricultural crop is or is to be planted. Some of the compounds are active in infested areas when applied to the above-mentioned land parts of plants, and can be applied as such.

The following are specific examples of formulations that may be utilized in accordance with the present invention.

A typical 5% powder (w/w) formulation is as follows.

Active Ingredients (100% Active Base) 5% Sodium (100%) 2% Powdered Sodium Alkylnaphthalene Sulfonate (75%) A typical Atakulay granular formulation is as follows.

Active ingredient 5% Atta clay 95% A typical sand core grain formulation is as follows.

FMC 75% base 6.64% Polyvinyl acetate 0.75% Water 1.00% Silica (20/40 mesh) 91.61% Ataclay granular formulation is prepared by dissolving the active ingredient in a volatile solvent such as methylene chloride and then Applying Attaclay to the sand by coating it with the resulting solution or by other methods well known to those skilled in the art and utilizing a solvent adhesive such as vinyl acetate to produce coated grains. can be created by

The compounds of the invention were tested for botanical activity in either a reagent formulation, as a solution of the active ingredient in acetone, or in a granular formulation. Activity against the root-knot nematode (MeloidHyne j, ncognita) was determined by placing the compounds in nematode infested soil at rates ranging from 25 ppm to 1.25 ppm. Some tomato plants were planted in soil infested with nematodes. The test was evaluated two weeks after planting to determine the degree of gall in the plant root soil indicative of the control provided by the test chemical.

The results, expressed as Knot 1ndex, are shown in Table II. The hump index is a mathematical designation that is assigned to an evaluation and has the following meaning:

Bump index Observed degree of control O No swelling - Complete control ~75% less swelling than control plants 2 ~50% less than control plants 9 galls 3 Than control plants ~ 25% less swelling 4 About the same as control plants ~ No control To indicate how close the degree of control is to 75% or 100% when the gall index is between 0 and 1, further as follows: It is subdivided.

gall index Degree of control 0.8 80% 0.5 90% 0.1-0.4 95-99% The results reported in Table II are the average of the gall index assigned to each test. The average hump index for each case where two or more different formulations or batches thereof are used is reported. The compounds of the present invention have a root knot (ro).
ot-kno, t) was extremely effective against nematodes.

The compounds of the invention may also be used to inhibit the growth of young corn plants (Tyl, enchorynchus clayt, o.
20 ppm to 5 ppm for prevention of damage caused by
It was also tested by soil incorporation at a range of rates. 15ppm
All compounds tested were effective in controlling growth-arresting nematodes, except for compound 12, which showed no control. Percent inhibition ranged from 52.9 to 99.8%.

The compounds are also effective against the damage nematode (Pratyl) of young pea plants.
Enchus penetraus) was similarly evaluated for control of damage. The compounds were highly effective in controlling lesion nematodes, except against compound 9, which showed no control at 15 ppm. At 15 ppm control, the compound is 27
．． The control values ranged from a low of 6% control (compound 21) to a high of 92.6% (compound 20).

Table ■ 1 5% powder 25 0.0 0.0 0.010 −
2.01.0 5 --4.0 2 5% powder 25 0.0 0.0 -10 - 0
．． 653.5 5 - - 4.0 3 5% powder -250,00,0- 10-0,650,12 5--1,25 2,5--3,75 45% powder 25 0.0 0. 0 -10 - 0.
250.0 5 - 0.8 2.5 - 4.0 5 5% powder 25 0.0 0.0 -10 - 0
．． 40.5 5 - - 1.25 2.5 - - 3.25 Table ■ (Continued) Rub compound Application rate Prescription or test number u] □Upper grade 6 5% powder 25 0.25 0.0 - -10
'-0,650,0- 5--0,02,5 2,5--0,04,0 75% powder 25 0.40 0.0 -10 - 0
．． 73 1.0 j --1,0 2,5--4,0 85% powder 25 0.0 0.0 -10 - 0.
0 0.62 5 − − 2.0 2.5 −−3.8 9 5% powder 25 0.0 0.0 −10 − 0
．． 0 4.0 10 5% powder 25 0.25 0.0 -1.0
- 0.5 0.25 5 - - 3.0 2.5 --4.0 Table ■ (continued) 11 5% powder 25 0.0 0.25'-10-0
,950,5 5--1,5 2,5--4,0 125% powder 25 0.0 0.0 -10 - 0
．． 0 0.37 5 - - 1.25 2.5-- 4.0 13 5% powder 25 0.0 2.0 -10 -
3.0 0.75 5 - - 4.0 14 5% powder 25 0.4 0.0 -10 -
0.250.37 5 - - 0.9 2.5-- 4.0 15 5% powder 25 0.0 0.0 -10 -
0.0 3.0 5 - - 3.0 2.5 -4.0 Table ■ (continued) 16 5% powder 252.0 1.5 -10 - 3
．． 5 - 17 5% powder 25 0.25 0.0 -10 -
0.5 Q, 62 5 - - 1. 0 2.5 - - 4. Q 18 5% powder 25 2.0 1.010' -1
,75 195% powder 25 0.5 0.13 -1.0 -
0.78 1.20 5 - - 4.0 20 5% powder 25 0.0 0.05 Q, 010
- 0.5 0.75 0.855, - - 0.
83 2.75 2.5 - - - 4.0 5% sand grains 25 - 4.0 5% atta 25 - 1,5 Clay grains 10 - 3.0 5 -4.0 Table ■ (continued) Kobu P ″ Compound Application rate Prescription or test number side 1 Prescription type Haku-ichi'-1 Meshi] - 215% powder 25 2.0 0.2 - -10 -
0.6 2.0 0.87 5 - - 2.75 3.25 2.5 - - 3.0 /1.0 22 5% powder 25 1.0 0.7510 - 3
．． 0 23 5% powder 25 0.9 0.0 -10 -
0.58 0.95 5 - - 2.25 2.5 - - 1.75 24 5% powder 25, 1.50 0.910 -
2.0 25 5% powder 25 0.35 0.0 - -10
- 0.2 1.25 - 5 - - 1.750.95 2.5 - - 3.75 3.25 1.25 - - - 4.0 26 5% powder 25 2.0 0.7g10 - 2
．． 25 Table ■ (continued) 27 5% powder 25 0.0 0.0 0.9510
-1.0/1.0

Claims (1)

[Claims] In the formula, R is hydrogen, methyl or chloro. R1 is hydrogen or methyl. R2 is hydrogen or methyl. R3 is hydrogen, halogen or methyl. R4 is hydrogen or halogen. R''' is hydrogen, halogen or lower alkoxy. R6 is hydrogen or halogen, except a) When R' is methyl, R, R'', R' and R6 are each hydrogen and RS is hydrogen or bromo, R3 is other than methyl. (b) R” is: A chill, R, R2, R' and Rs
are each hydrogen and R6 is hydrogen or bromo, R3 is other than bromo. (c) When R'' is methyl and R, R2, R' and R5 are each hydrogen, R4 and R6 cannot both be chloro. (d) When R' is methyl and R, R2, R ' and R6 are each hydrogen, provided that R3 and R5 are not both chloro. 2. The compound of claim 1 when R, R1 and R2 are each hydrogen. 3 , R is methyl or chloro, and R1 and R2 are each hydrogen. 4. The compound of claim 1, where R2 is methyl and R and R1 are each hydrogen. 5゜( 1) l-(4-chlorophenyl)thiocarbamoyl-
2-phenyl-3-pyrazolidinone (2)]-(]/I-ethoxyphenylthiocarbamoyl-2-(4-methylphenyl)-3-pyrazolidinone (3) 112-chlorophenyl)thiocarbamoyl-2
-(4-methylphenyl)-3-pyrazolidinone (4)
1-(3-chlorophenyl)thiocarbamoyl-2-(
4-methylphenyl)-3-pyrazolidinone (5) 1-(4-chlorophenyl)thiocarbamoyl-2-(4-methylphenyl)-3-pyrazolidinone (6) 1-(2-bromophenyl)thiocarbamoyl-2- (4-Methylphenyl)-3-pyrazolidinone (7) 1-(3-bromophenyl)thiocarbamoyl-2-(4-methylphenyl)-3-pyrazolidinone (8) 1-(4-bromophenyl)thiocarbamoyl- 2-(4-methylphenyl)-3-pyrazolidino(9
) 1-(2,5-dichlorophenyl)thiocarbamoyl-2-(4-methylphenyl)-3-pyrazolidinone (10) 1-(5-chloro-2-methylphenyl)thiocarbamoyl-2-(4-methylphenyl )-3-pyrazolidinone (11) 1-(4-ethoxyphenyl)thiocarbamoyl-2-(4-chlorophenyl)-3-pyrazolidinone (12) 1-(2-chlorophenyl)thiocarbamoyl-2-(4-chlorophenyl) -3-pyrazolidinone (13) 1-(3-chlorophenyl)thiocarbamoyl-2-(4-chlorophenyl)-3-pyrazolidinone (14) 1-(4-chlorophenyl)thiocarbamoyl-2-(4-chlorophenyl)-3 -Pyrazolidinone (15) 1-(2-bromophenyl)thiocarbamoyl-2-(4-chlorophenyl)-3-pyrazolidinone (16) 1-(3-bromophenyl)thiocarbamoyl-2-(4-chlorophenyl)-3 -Pyrazolidinone (17) 1-(4-bromophenyl)thiocarbamoyl-2-(4-chlorophenyl)-3-pyrazolidinone (18) 1-(3-fluorophenyl)thiocarbamoyl-4-methyl-2-phenyl-3 -Pyrazolidinone (19) 1-(2-chlorophenyl)thiocarbamoyl-4-methyl-2-phenyl-3-pyrazolidinone (20) 1-(4-chlorophenyl)thiocarbamoyl-4-methyl-2-phenyl-3-pyrazolidinone (21) 1-(4-bromophenyl)thiocarbamoyl-4-methyl-2-phenyl-3-pyrazolidinone (22) 1-(2-iodophenyl)thiocarbamoyl-4-methyl-2-phenyl-3-pyrazolidinone (23) 1-(2,5-dichlorophenyl)thiocarbamoyl-4-methyl-2-phenyl-3-pyrazolidinone (2/I) 1-C4-chloro-2-methylphenyl)
Thiocarbamoyl-4-methyl-2-phenyl-3-pyrazolidinone (25) 1-(5-chloro-2-methylphenyl)thiocarbamoyl-4-methyl-2-phenyl-3-pyrazolidinone (26) 1-(phenyl ) Thiocarbamoyl-5-methyl-2-phenyl-3-pyrazolidinone (27) 1
A compound selected from the group consisting of -(4-chlorophenyl)thiocarbamoyl-5-methyl-2-phenyl-3-pyrazolidinone. 6. Claims in admixture with at least one agriculturally acceptable adjuvant, diluent or carrier], 2,3
．． A nematicidal composition comprising a nematicidally effective amount of compound 4 or 5. 7. A method for controlling nematodes in agricultural and horticultural crops, which comprises applying a nematicidal amount of a compound according to claim 1, 2, 3.4 or 5 to a disturbed area.